Process of purifying water.



PATENTBD DEG. 12, 1905. 'J. F. WIXFORD. I PROCESS -OF PURIFYING WATER. APPLICATION lFILED JUNI: 20, 1905.

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W bnassee N0. 807,008. PATENTED DEC. 12, 1905-. J F. WIXFORD.

PROCESS OPPURIFYING WATER.

APPLIGATION FILED JUNE 2e, 1905.

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'Wihnlesszs UNITED STATES PATENT euries.

Jenn F. WIXFORD, 'or sT.` Louis, Missouni. Princess oF-PUmr-Yme WATER,

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Specification of Letters Patent( Patented n'e.' 12',- 1905.

Odntluuetion of application VSerial No1225,611, illed September 23, 1904. This application filed June 26, 1905,Se1-ia11lo. 266,948.

` 1 Be it know'n'thatl, J onN F.WIxFonD,'a citi- 4zen of the United States, and a resident ofthe city of St. Louis,.State of Missouri, have invented a new and useful Process of Purifying Water, of which the following is a specification.

'fit is noted-that this application is in `continuation, in part, of my earlierapplioation,"

Serial No. 225,611, filed September 23, 1904..

urally contained inthe water in aid of thereagents adde'd thereto, also to shorten the` time required for the settling of the sediment,

also to eliminate the danger'of leaving a discoloringagent in the clarified water, also to" attain other advantages hereinafter speciiied.

Many I uatura'l vvaters, such. as the water of the lMississippi river, contain in solution a considerable proportion of bicarbonates of calcium and magnesium and containin suspension large quantities of mineral and or- 'game matter, and.`m v processjis especiallyv adapted for the treatment of such Waters.

4My invention consists principally in con.- verting thexdissolvedl carbonatos intov insoluble compounds in theA presence of a coagulaut. It also consists in generating a coagulaut in the water. and converting the dissolved carbonatos into insoluble compounds. It also The mechan consistsin the hdetails hereinafter described and claimed.

In the accompanying drawings, which 'form' part of this speciiicationand wherein like lsymbols refer to like partswherever they occur, Figure lis a plan-view of a system adapt- .ed for usef with my process, and Fig.4 2 is a 4 1 vertical sectional view' through the settlingbasin of such .SyStem ical system illustrated in the acjcomp'anying drawingscomprises an intakel tower 1, located in the river or. other source of water-supply 2; a' conduitV 3, leading from vthe intake-tower to pumps 4, located on shore;

two conduits '5"6, leading from the respective pumpsto separate delivery-wells? 8; conduits 9 10, leading yfrom the delivery-.wells to the flow pipe or'. conduit 11 vwhich communicates with one or l'more settling-basins 12, and one r more outlet-pipes 13, leading from the settling-basrisftothe distribution system.

I In additiento the. foregoing arrangement the system shown in the drawings comprises $5 a clear-Water pipe llt, leading from the distribution system through a digester or solution-tank 15 and into one of the delivery-Wells 7.- It also comprises a-'second clear-water pipe 16, leading'from a source of'fhotwater 6o y through a second digester or slutidn-tank 1 7,

especially arranged for the preparation of lmilk of lime, and into the second of the delivery-Wells.

after stated. various reagents may be used but for the sake of. simplicity of description I shalliirst describe it as practiced with ferro us sulfate. f

At definite `intervals measured quantities of 7o ferrous sulfate areplaced in the digesterl 15,

- through which a constant stream of water is iiowing continuously. l 1n consequence o f this arrangement a solution of ferrous sulfate of constant'strength is continuously prepared 75y and {"ed into the delivery-welllthe same` time measured quantities of lime are fed at .regular intervals intol the .lime-digester 17, -which is provided-with mechanical --agitators l and through which a stream of hotI Water is 8o flowing continuously.l By this arrangement a constant amountof hydrate of lime, mostly inthe form of milk of lime, is continuously preiared and lfed lintothe second deliverywe 8, n?

The reason for using hot vvater in preparing the milk of lime is that it is impracticable to slake limein a running stream of cold wathoroughly mixed with the rawv `Water therein. During the time that the Water takes to iiowirom the delivery-wenste the point 95 action of the ferrous sulfateiswith thedissolved carbonates, which reaction results in theA formationgof" ferrous` bicarbonate., The `roo principal reactionsof the lime are, first, its reaction with the dissolved bicarbonates', which reaction results in the form-ation'of insoluble normal carbonate, and, second, a coagulating action Auponthe particles oflclay in suspenv105 sion.v Much of the lime dissolves and remainsl in solution.- The mov-ement of thewater from the delivery-wells to thesedimentation-basin inthe practice of my process as herein- 65 The-water in thedelvery-Wells 7'8'is vio- 9o lently agitated, whereby the reagents. added .thereto in the respective delivery-wells are A produces asufflciently violent agitation to prevent the deposition in the conduits 9 10.1 1 of precipitates and suspended matter.

When the two streams-namely,those treated withthe yferrous sulfate and the hydrate of lime, respectively/ .unite, there are two principal reactions. One is the reaction :the lime withthe ferrous bicarbonate, resuiting in the formation of ferrous l1ydrate,and the lother is the reaction ofthe lime upon the dissolved carbonates, resulting in the formation of the insoluble 'normal carbonates.I The ferrous hydrate quickly oxidizes to-ferric hydrate. These reactions are accompanied with other reactions of minor importance. The

. -most important of the minor reactions appears to be the reaction of the lime with the clay in suspension, which produces a fiocculation of t lcarbonate of calcium is .a very finely divided l tation suflicient to prevent sedimentation un-l white precipitate which forms slowly and re'- mains in suspension for a long time. As stated above, thewater is kept in a state of agitil it reaches the settling-basin. Consequently the large heavy particles of iron precipitate.

kept in suspension in the moving water constitute nuclei around which agglomerates the lighter and late-forming carbonate of calcium aswell as the organic and mineral matter originally in suspension or precipitated by the chemical reactions.

point where the two streamsl come together to the settling-basin should be sufficient to require from three to fifteen minutes time for the water totraverse it. When the water enters the settling-basin, the agglomerated particles settle rapidly, leaving the supernatant water very' clear. A

The probable reactions of the lime are as follows: All of the free carbonio acid (CO2) is rapidly converted into insoluble normal calcium carbonate. and all of the ferrous bicar-v bonate is rapidly converted into insoluble calcium carbonate` and ferrous hydrate. Calcium bicarbonate is changed into insoluble normal calcium carbonate, bicarbonate of magnesia is changed to insoluble. magnesium carbonate and magnesium hydrate, and some of the silicates in the water are changed to calcium silicate and probably some other insoluble silicate. It is to be understood, of course, that the foregoing reactions are accompanied with reactions of lime uponother matter, such as sulfate of'magnesium or organic matterVif any is presentin the water.

On account of the above-mentioned reactions with the bicarbonates and silicates 0ccurring' principally after the free carbonic acid (COQ) and the ferrous sulfate have been cornpletely satisfied the amount of the carbonates In order to permit thisr action, the-length of the conduit 11 from the4 and silicates affected will' be proportional to the amount of lime in excess of that needed to satisfy the free carbonio acid and thei'ron.

. Usuallyit is unnecessary for clarification purposes to react upon all of the carbonates and silicates in the water, and it is n ot usually desirable to entirelyeliminate them from drink'- ing-waters.

On 'account of its great coagulating power and heavy weight vferrie hydrate constitutes the'principal coagulant and tends to produce rapid precipitation; but the hydrate of magnesium and some of the in'soluble'silicates are also coagulants and operate in conjunctionA with the ferrie hydrate. i

The. ferrous sulfate' vis intended vto beconverted into a coagulant, and itis obvious that the amount of coagulant required will increase as the amount of suspended matter increases' and as such matter is lighter and more finely divided. As the sulfates of calcium and magnesium resulting from the addition of ferrous sulfate 4remain in the clarified water, it is advisable tovlimit the amount of ferrous sulfate to what is needed (when supplemented by the otherv coagulants) to producev the desired co" agulating action. In the case of water from the' Mississippi river'at St. Louis one-half of a vgrain of ferrous-'sulfate crystals (or their equivalent of the anhydrous form) to'on'e gallonvof water is'sufhcient when the river is clearest, whereas three grains or more of crystals (or their anhydrous equivalent) may be necessary to promptly precipitate Athe suspended vmatter when the riveris very turbid. On `account of the extreme fineness of the clay particles in the Water it is probable that certain portions thereof act in the manner of a vcolloidalsolution and that the limereacts thereon as', such. The amount of lime to be ladded increases with the amount of free carbonic acid and with the amount of iron added to the water. 'The amount of lime also in- IOO creases proportionately tothe amount of carbonates (and silicates) remaining in the 'Water after the free and uncombined carbonio acid (CO2) and ferrous sulfate shall have been satistied. In the case of' the Mississippi-river water Aat St. Louis the amount of lime required for thev best and most economical results varies from about four grains to the gallon of water to eight or even more grains.

Theamount o f lime that can be usefully employed in this processv for clarifying and elimination purposes is determined by two factors: first, the 'amount of such matter in the natural water (whether in solution or in suspension) as reacts with 'lime' and, second,

IIO

, the same, however, when the ferrous sulfate is added first, for while the ferrous sulfate first reacts with the bicarbonate of calcium in .the raw water, and thereby converts part o'f the lime into the subsequently'inert formof calcium sulfate, the same reaction vproduces ferrous bicarbonate,4 which requires to satisfy 1t as much llme as the amount rendered inert as calcium sulfate. `Any excessof lime above the total of these two factors will result in making the clarified water caustically alkaline, which condition is usually undesirable.

' sulfate is added first and is followed by an supply systems.

amount of lime less than. the total amount of these two factors the clarified water will retain a portion of the salts. naturally belonging thereto. AAs it is usually desirable to retain a portion of such salts, the proper amount of lime to be added in the practiceof my proc# ess under ordinary conditions is approxi-v mately the same as the amount of the first factor above stated-namely, they amount that can be taken up by the raw, water. This amount may be determined by adding hydrate of lime to the raw water in various proportions and after the lapse of some hours testing for alkalinity. For this purpose nitrate of silver is used (in the absence of strong sunlight) as an indicator, and the amount of lime required to be added to the raw water to show A a brown precipitate immediately upon the addition of nitrate of silver thereto after the lapse of several'hours from the time when the lime was added is the amount of lime that reacts with or is taken up by the matter in the Water,land this amount usually furnishes the proper proportions for use in municipal watergrai'ns per gallon of water, depending upon i the condition' of the water.

.y so

L-4 clear ameasured volume is decanted andsi'lver` 'nitrate added thereto in excess of thequantity' A more rapid method of' ascertaining the amount of lime that can be taken up by the raw water is as follows: To a measured quan.`

tit-y of water to be treated there is added a ,measured quantity of lime-Water more than sufficient to react with the constituents of the water. and settling until the water is moderately needed to combine with any chlorids the water may contain, whereby a brown precipitate of.

On the other hand, when the ferrous val. Vthrough the ferrous sulfate, and as the mass of water {iowing through 'the ferrous sulfate- In the casel of the Missis. sippiriver water at St. kLouis the proper' amount' of lime will vary from four to eight After agitation for'several minutes and will quickly turn black in strong sunlight. This method of ytitration with decinormal sulfuric acid may be 'advantageously varied as follows: After adding the lime-water to the raw ,Water'and agitating and settling, a measured volume of the treated Water is filtered and a few drops of phenolphthalein addedV thereto to give it a red color. Decinormal sulfuric acid is thenadded from a buretteuntil the red color disappears. The amount of deci-normal sulfuricvacid used measures the 'excess of. lime in the sample, and this deducted from the total amount of lime originally added gives` the amount of lime taken up bythe water.

It is important that the lime and iron should v` y be thoroughly mixed with the-water and uniformly distributed therein in definite propor tions. For this pu rposethe followingv method is most satisfactory in 'large plants: A quantity of ferrous sulfate equal to the supply required for the vtreatment of the amount of 'i waterissuing from thepumpspipe during a i predetermined interval is placed in the receptacle or digester 15, through which a constant volume of water is continuously passing. At y the endfof the first` interval an additional amount of ferrous sulfate s uiiicent for'the treatment' of the water for the next interval lis added to the receptacle, and this addition of ferrous sulfateis repeated for each inter- Preferably the water flows upwardly is uniform the accumulation of ferrous sulfate in the receptacle will soon reach such an amount as to` render the rate of solution of ferrous sulfate substantially uniform-that is to say, that the amount of ferrous sulfate dissolved 'in the water during theA interval will equal the amount of ferrous sulfate added to' the tank for said interval. rlvhe v'olum'e'of waterpassing through the receptacle is preferably regulated'so'as to require a large mass of ferrous sulfate in the receptacle to bring about a periodic solution equal to the mass of vthe ferrous sulfate added for the period, in

which case the rate of solution is substantially uniform throughout theentire period. '.lhe amount of ferrous sulfate to be added may be varied from time to time according as the w..l ter supplied by the pump varies.

The water i iiowing from the receptacle containing the ferrous ysulfate is delivered directly into the water from vone or more of the pumps, pref erably at suoli point as to secure a thorough distribution of the iron throughout the water before it reaches the settling-basins and before Vthelime is added thereto'. Obviously,I however, it is permissible to make up the ferrous-sulfate solution in advance and deliver such solution `from the storage-tank in more or less concentrated form.n

The liine is preferably u Eed in the form of milk of lime. For this' purpose measured quantities of lime are placed in a receptacle or digester 17, through which a constant volume of hot water is continuously iiowing, and the lime is continuously agitated in said receptacle. The water containing thehydrateof lime is delivered directly into one stream of the water to be treated. .At predetermined intervals additional measured quantities-oflime are placed in the receptacle, so that eventually the amount of lime issuing from said receptacle becomes substantially uniform.

According to the foregoing description the lwater to be treated isdivided into two streams,

to the smaller of which the vlime is :added and to the larger of which the ferrous sulfate is added. In consequence of this arrangement the ferrous sulfate is converted into ferrous bicarbonate, and the lime is mostly in solu- .tion by the time the respective streams containing these reagents unite. The two reagents may, however, be added to the same stream,

in which case the ferrous sulfate is prefer-v ably added to the .water before the water reaches the point where the hydrate of lime is added, so that the white precipitates of the ylime reactions are formed after and upon the around. Consequently when the water reachesl the settling-basin and becomes quiet the sedimentation is very rapid. 4

In the purification of water in large quantities it is important to shorten the time required for settling as much as practicable, and

.this object is attained by my invention, wherein the coagulant action of the ferrie hydrate in conjunction with the hydrate of magnesia andy the insoluble silicates causes the rapid settling .of the light precipitate of carbonate of lime and the 'fine suspended matter which would otherwise require a long period of settlin Ogn account of the large demands made upon -the Water-supply' systems it is frequently impracticable to allow the water to'stand long enough for all of ythe suspended matterto settlc, in consequence of which thewater from the settling-basin contains more or less fine particles in suspension. This fine matter is usually either removed by iltration or passes into the distribution-pipes. In other lprocesses, where-iron is used for purifying water, this suspended matter sometimes discolors the water, but always causes the water to stain whatever it comes in contact with. The necessity for a filter and the danger of staining conathos stitute the principal objections to the use of l iron for purifying water.y By my process, however, the necessity for a filter and the danger of the water staining are both eliminated, the ilter beingvunnecessary by reason of the strong coagulating action and rapid settling above described and the staining power of the ferric hydrate being removed byvreason of its particles hav-inga thick whitish coating o'f carbonate of lime and hydrate of magnesia and other matter.

Another advantage of my invention is that the Asoluble silicates are notonly eliminated, but actually utilized for the elimination of other matter.

Another advantage is that substantially all of the bacteria and other organic matter are eliminated.

My process admits of considerable modification without departing from my invention.v Thus other soluble mineral salts of iron may be substitutedl for thev ferrous sulfate in which case the carbonate of lime is changed into the corresponding salt of calcium instead ofthe sulfate, and such salt either remains permanently in the water if it is soluble or is precipitated if it is insoluble. The particular advantage of iron sulfate, however, is lits cheapness. So, too, instead of iron salts other -metal sulfates may be used, such as sulfate of copper, zinc, manganese, or aluminium.

1. The process of purifying water 'which consists in adding thereto a solution of a metallic sulfate and a quantity of lime approximately equal to the amount of lime required to be added to the raw water to make it give a caustically-alkaline reaction.

i2. The -process of purifying water which consists in adding thereto separately a solutionof a metallic sulfate and a vquantity of -lime approximately equal to that required to be added to the raw water to make itindicate caustic alkalinity after a considerable time when tested with lnitrate of silver.

3. The process of purifying water which consists in adding thereto' separately a solution of a metallic sulfate and a quantity of 'lime approximately equal to that required to make the raw water indicate caustic alkalinity after a considerable time when tested with nitrate of silver, and keeping the water agitated for severalminutes and then permitting sedimentation.

l4:. The process of purifying waterv which consists in adding thereto a solution of a mineral salt of iron and treating it with hydrate of lime, the proportion of lime being approximately the same as that required to be added to the raw water to make it indicate caustic alkalinity.

'5. The process of purifying water which consists in adding thereto a solution of a mineral salt of iron and treating it with hydrate of lime, the proportion of limebeing approxi- IOO portion of one grain of ferrous sulfate and six grains of hydrate of lime per gallon of Water,

-f thelime being ,added to the main .stream at a pointbeyond the point of admission of the 5- Sulfate and in excessof the amount required to satisfy the free carbonio acid and the sulfatefinthe Water, saidreagents beingl added rby means ,of streams of water running con- 'rinuously through' masses of the respective re-4 io ed at intervalstosecure uniformity of distri- :xgents to which, measured quantities are add- .bution.

The processo-fi purifying Water Whichcousists in vadding to a'stream of Water to be purified approximately one grain of ferrous sulfate per gallon and approximately six grains of hydrate of lime per gallon, and then permitting such Water to settle, the lime being added to such stream` at a point beyond 2.0.

the point of admission of the ferrous sulfate.

.20. The process of 'purifying Water which consists in adding to a stream of Water to be purified approximately one grain of ferrous sulfate per .gallon and approximately siX grains of hydrate of lime per gallon, keeping the Water thus treatedin a 'state of agitation for several minutes, and then permitting such of hydrate of lime per gallon, causing the v water of said streams to unite soon after the addition of said reagents thereto, keeping the commingled Water in .agitation for several minutes and then permitting such Water to settle.

22. The process of purifying Water which consists in addingthereto while in motion approximately one grain of ferrous sulfateand approximately six grains of hydrateof lime per gallon, theferrous sulfate being added before the lime by means of a stream of'water flowing continuously through a mass of ferrous sulfate to which measured quantitiesare added at measured intervals.

JOHN F, WIXFORD.

Witnesses:

FRED F. REIsNnR,- J B. MEGOWN. 

